Phenol modified polyacetals



2,902,470 Patented Sept. 1, 1959,

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2,902,470 PHENOL MODIFIED POLYACETALS Bernard H. Kress, Lafayette Hill,Pa., assignor to Quaker Chemical Products Corporation, Conshohocken,Pa., in corporation of Pennsylvania No Drawing. Application November 30,1956 Serial No. 625,242

6 Claims; (Cl. 260-47) The present invention relates to novel phenolmodified polyacetals and to their preparation and uses. My phenolmodified polyacetals difier in properties and in uses fromphenol-aldehyde compositions known to this art because of the propertiesimparted by the polyacetal groups. Thus, my polyacetal compositions giverise to flexible resins of the thermosetting type which have not beencapable of achievement heretofore. These resins in cured form are oflight color, thus permitting the preparation of light or pastel coloredcoating compositions, molding compositions and the like. Because of goodcolor, use of these compositions is practicable in the finishing oftextiles. They are particularly useful in adhesive applications,especially as binding agents for cellulosic materials and rubber.

I may make my polyacetals by condensing a suitable reactive phenol witha suitable polyacetal by use of heat and catalyst, although the latteris not required in all cases. The polyacetals used for this purposeinclude aldehyde condensation products of alkylene and polyalkyleneglycols possessing alkylene groups containing from 2 to l carbon atomsin a straight chain. 'Such glycols include, for example, ethylene,propylene, trimethylene, and butylene glycols, pentanediols,hexanediols, octanediols, decamcthylene glycol and the like, diethylene,dipropylene, dibutylene glycols, tn'ethylene, tripropylene andtributylene glycols, tetraethylene glycol and the like, andpolyethylene, polypropylene and polybutylene glycols of molecularweights equal to about 200, 400, 1000, 1500 and 4000, such aspolyethylene glycols and Carbowaxes made by Carbide and Carbon ChemicalsCompany.

The aldehydes which may be used in making these polyacetals includeformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,crotonaldehyde, valeraldehyde, hexaldehyde, heptaldehyde and Z-ethylhexaldehyde, or their polymers, precursors or simple acetals. Aromaticaldehydes, such as benzaldehyde and furfural are of use in thesepreparations. Substituted aldehydes, such as chloroacetaldehyde, hydroxypivaldehyde and similar halogen and hydroxy substituted aldehydes oracetals may also be used. Aliphatic and aromatic dialdehydes may also beused. Thus, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde,adipaldehyde, terephthaldehyde and higher dialdehydes are useful. Inaddition, I may use their precursors such as dialkoxytetrahydrofuranesand alkoxydihydropyranes or the simple acetals of the dialdehydes inthese reactions, Hydroxyaldehydes, such as hydroxyadipaldehyde are alsouseful in these preparations. In general, I may use any aldehydecontaining from 1 to 8 carbon atoms in monomeric form, includingheterocyclic aldehydes such as furfural, methyl furfural, ethyl furfuraland the like, or carbocyclic aldehydes such as tetrahydrobenzaldehydeand the corresponding hexahydro compounds. Phenols useful in thesepreparations include phenol, cresols, xylenols, dihydroxy benzenes suchas resorcinol, hydroquinone, and catechol, orcinol, pyrogallol,phloroglucinol, hydroxyquinol, dihydroxy diphenyls,para-isopropylidenediphenol, alpha andbeta-naphthol, hydroxyanthraquinone and dihydroxy anthraquinone and the like. Alkylsubstituted phenols and aromatic substituted phenols, can be used. Thus,t.amyl phenol, nonyl phenol, tridecyl phenol, octadecyl phenol,pentatriacontyl phenol and cardanol derived from cashew nut shell oilcan be used in making my condensation products. Similarly p-phenylphenol is of value in obtaining water-insoluble products. In general, Imay use any phenol containing a single or a plurality of aromatic nucleibeating at least one hydroxyl group and one or more side chainscontaining from 1 to 35 carbon atoms. Phenol derivatives such aseugenol, isoeugenol and the like may also be used.

Further details of my invention will be apparent from the followingillustrative examples. My phenol modified polyacetals may be prepared byseveral different methods. For example, I may first prepare suitableintermediate polyacetals as disclosed in my co-pending applicationSerial No. 403,056 filed January 8, 1954, now Patent No. 2,786,081.These acetals are then modified with a suitable reactive phenol toproduce the products of this invention. The intermediate acetalsdesignated as products A to E hereinafter were first prepared asfollows, the reactants being given in parts by weight:

INTERMEDIATE PRODUCT A These compounds were heated under reflux with amoisture trap inserted between the flask and the reflux condenser. After18 parts of water of reaction were withdrawn from the reaction mixture,it was heated in vacuo with agitation to remove toluene. Underconditions of 20 min. of mercury and at temperatures up to C. novolatile organic condensation. product was obtained, The resultingproduct was then neutralized With dilute NaOH solution to a pH of 7. Theresulting intermediate acetal condensation product was completelysoluble in water and in toluene. It had a faint ethereal odor and wassomewhat viscous. It was free of formaldehyde odor under normal roomconditions. The product had a molecular weight'of 480 (Rast) and ahydroxyl equivalent of 220 which indicates it had a linear polymericstructure. It had a specific gravity of 1.155 at 34.5 C. The refractiveindex was N =l.462. The molecular weight and hydroxyl equivalent of thecondensation product of this product indicate that it possesses apolymeric structure, containing an average of four diethylene glycolunits, as shown in the following formula:

where X and Y may stopper.

Such a preparation is illustrated in the following product:

INTERMEDIATE PRODUCT B Parts Diethylene glycol 101 .Betam bpxye han l 4lfara formaldhyde (91%) 30 --.--.-'."'-'7T 'T- Sulfuric acid (99%) 0.1

The above materials were reacted as under product A to These reactantswere treated as under product A. The

viscous liquid forms a crystalline mass below OT'C. The "1) came: issoluble in water or toluene and has a faint "etlitli'r'eal odor; I p

Tlie 19615 used in the preparation of these polyacetal's may be replacedin part with minor amounts of guy-hymn alcohols containing from 3 tocarbon atoms andffom 3 to 6 liydro'xyl groups, such as glycerine,trimethylol ethane, tr'im'ethylol propane, pentae'rymnwi, sorbitol,ma'nnitol, butane triol, hexanetriol, alpha-methyl glucoside anddipentaerythritol. Such polyhydric alco- -'hols may be used inquantities up to equirnolar amounts of the glycol or polyglycol employedin preparing my polyacetals as shown in the following example:

INTERMEDIATE PRODUCT D Parts Diethyle ne glycol 80 Sorbitol crystrlline;32 Parafornialdehyde (91%) 30 .Toluene. V

Sulfuric acid (99%) 0.1

The product after treatment as under product A is a crystalline mass atroom temperature, soluble in toluene and in Water, and with virtually noodor.

. I Mixtures of aldehydes and dialdehydes may also be used to give thefollowing product:

INTERMEDIATE PRODUCT E I 7 7 Parts Die'thyle'ne glycol a 106Parafoim'aldehyde (91%) 52 Glyoxal (30%) 39 Toluene" I 20 Sulfuric acid(99%) 0.1

Example 1 Parts Intermediateproduct-A 80.5 Phenol; 47 Zinc chloride 0.2

The matte was heated with agitation at 110 'c; i

glyco'ls mayalso be used to 4 about an hour to yield a viscous lightyellow product which was soluble in water.

Example 2 Parts Intermediate product A 59.5 Water 25.5 Resorcinol 55p.Toluene sulfonic acid 0.4

Example 3 Parts .P n' 41 Diethylene glycol v p 53 k 'i Barafornialdehyde(91%) 33 Toluene 30 p.Toluene siilfonic acid 0.3

The mixture was refluxed until 15 parts of water was removedazeotrop'ically. The toluene was evaporated in 'vacuo to leave a viscousalmost water-white liquid.

The products of Examples 1 to 3 have many valuable uses. Thus, they maybe used in imparting hand and diniensional control to cellulosic fabricsas shown below. Example 4 A'padding solution was made up as follows:5.0% condensation product described in Example 1 0.75% chloride 2.25%diglycolic acid 920% water A light-weight rayon challis material whichhad been bleached and scoured was marked with a Sanforize Test Marker.The fabric was then passed through the padding solution and rolls twice.The padder was adjusted for wet pickup. The fabric was then placed on aframe so as to hold it to the dimensions it possessed beforeimpregnation and dried in a hot air oven at 82 C. The fabric was thencured at temperatures of C. for '5 minutes. The treatment was repeatedon another sample of challis with 5% of the product of Example 2.

The following test results were obtained:

. 1 Wash 1 1 Wash 5 Product Warp Warp Shrinkage, Tensile, percent Lbs.

Ex. 6 0.0 31.0 Full hand. Ex. 7 0.1 33. 3 Do. Untreated 8.1 43. 3 Limp.

1' AATOQ 1952 14-52. 1 Fed. Spec. COO-T-lQIB-Methbd 5l022 width.

Example 5 The product of Example 1 in 10% concentration was 5. 250 F.for an hour to yield a rubbery transparent product suitable for use asan adhesive in bonding cellulosic fabrics and rubber.

Another use of my phenol modified polyacetals is their application intreating cellulosic tire cord in any stage of its manufacture in orderto obtain superior adhesion to rubber. Additionally dimensional controland limited swelling of the tire cord so treated is of value inincreasing the life of the tire.

The following example is illustrative of such treatment:

Example 7 The product of Example 2 was incorporated in a finishing bathof the conventional type used for treatment of viscose yarn. Theconcentration of the resorcinol and the period of immersion of the yarnwere adjusted so that the yarn after drying in the usual mannercontained 1 percent of resorcinol. The treated yarn was then doubled toform a 2/1650 denier cord and heated in an oven for 30 minutes at 125 C.in order to dry the cord and to cure the polymeric acetal. The cord wasmade up into a weftless fabric, coated with a layer of vulcanizablerubber compound by calendering and vulcanized in the usual manner.

The phenolic modified polyacetals of this invention are also suitablefor use in coating compositions, laminating compounds, molded andextruded plastics, printing ink formulations, adhesives, magnet wirecoatings, impregnating compositions for paper, vulcanized fiber andother porous sheet materials, ion exchange media and, in general, to awide variety of uses known to the art of phenolic resins where theunique flexibility of cured phenolic-modified polyacetals makes theirapplication invaluable. My polyacetals are particularly effective fortreating cellulosic materials, such as natural cellulose, regeneratedcellulose, hydrolyzed cellulose acetate, paper and paper fibers,regenerated cellulose fibers, jute, hemp and the like.

I claim:

1. A phenol modified polyacetal condensation product comprising thereaction product of a previously prepared acetal prepared by reacting atelevated temperatures in the presence of an acidic catalyst at least onealkylene glycol selected from the group consisting of monoalkylene andpolyalkylene glycols in which the alkylene radical has 2 to 10 carbonatoms in a straight chain and at least one aldehyde selected from thegroup consisting of aliphatic, carbocyclic, and heterocyclic reactivealdehydes containing from 1 to 8 carbon atoms in monomeric form, with atleast one reactive phenol selected from the group consisting of phenolshaving one to three aromatic nuclei bearing one to three hydroxyl groupsand hydrocarbon substituted phenols in which the hydrocarbon radicalcontains 1 to 35 carbon atoms, said condensation product containing permolecule at least two polyoxyalkylene radicals derived from saidalkylene glycol and at least two alkylidine radicals derived from saidaldehyde.

2. A phenol modified polyacetal condensation product as defined in claim1, modified by at least one polyhydric alcohol containing from 3 to 10carbon atoms and from 3 to 6 hydroxyl groups.

3. A phenol modified polyacetal condensation product comprising thereaction product of a previously prepared acetal prepared by reacting atelevated temperatures in the presence of an acidic catalyst diethyleneglycol and formaldehyde with phenol, said condensation productcontaining per molecule at least two polyoxyalkylene radicals derivedfrom said glycol and at least two alkylidine radicals derived from saidaldehyde.

4. A phenol modified polyacetal condensation product comprising thereaction product of a previously prepared acetal prepared by reacting atelevated temperatures in the presence of an acidic catalyst diethyleneglycol and formaldehyde with resorcinol, said condensation productcontaining per molecule at least two polyoxyalkylene radicals derivedfrom said glycol and at least two alkylidine radicals derived from saidaldehyde.

5. A phenol modified polyacetal condensation product comprising thereaction product of a previously prepared acetal prepared by reacting atelevated temperatures in the presence of an acidic catalyst a dialkyleneglycol in which the alkylene radical has 2 to 10 carbon atoms in astraight chain and at least one aldehyde selected from the groupconsisting of aliphatic, carbocyclic, and hetero cyclic reactivealdehydes containing from 1 to 8 carbon atoms in monomeric form, with atleast one reactive phenol selected from the group consisting of phenolshaving one to three aromatic nuclei bearing one to three hydroxyl groupsand hydrocarbon substituted phenols in which the hydrocarbon radicalcontains 1 to 35 carbon atoms, said condensation product containing permolecule at least two polyoxyalkylene radicals derived from said glycoland at least two alkylidine radicals derived from said aldehyde.

6. A cellulosic material treated with a phenol modified polyacetalcondensation product as defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS2,128,894 Bond Sept. 6, 1938 2,293,805 Cooke et al Aug. 25, 19422,366,738 Loder et al Jan. 9, 1945 2,401,776 Rothrock June 11, 1946 iFOREIGN PATENTS 620,565 Great Britain Mar. 28, 1949 696,105 GreatBritain Aug. 26, 1956

1. A PHENOL MODIFIED POLYACETAL CONDENSATION PRODUCT COMPRISING THEREACTION PRODUCT OF A PREVIOUSLY PREPARED ACETAL PREPARED BY REACTING ATELEVATED TEMPERATURES IN THE PRESENCE OF AN ACIDIC CATALYST AT LEAST ONEALKYLENE GLYCOL SELECTED FROM THE GROUPS CONSISTING OF MONOALKYLENE ANDPOLYALKYLENE GLYCOLS IN WHICH THE ALKYLENE RADICAL HAS 2 TO 10 CARBONATOMS IN A STRAIGHT CHAIN AND AT LEAST ONE ALDEHYDE SELECTED FROM THEGROUP CONSISTING OF ALIPHATIC, CARBOCYCLIC, AND HETEROCYCLIC REACTIVEALDEHYDES CONTAINING FROM 1 TO 8 CARBON ATOMS IN MONOMERIC FORM, WITH ATLEAST ONE REACTIVE PHENOL SELECTED FROM THE GROUP CONSISTING OF PHENOLSHAVONG ONE TO THREE AROMATIC NUCLEI BEARING ONE TO THREE HYDROXYL GROUPSAND HYDROCARBON SUBSTITUTED PHENOLS IN WHICH THE HYDROCARBON RADICALCONTAINS 1 TO 35 CARBON ATOMS, SAID SAID CONDENSATION PRODUCT CONTAININGPER MOLECULE AT LEAST TWO POLYOXYALKYLENE RADICALS DERIVED FROM SAIDALKYLENE GLYCOL AND AT LEAST TWO ALKYLIDINE RADICALS DERIVED FROM SAIDALDEHYDE.